石油炼制与化工 ›› 2023, Vol. 54 ›› Issue (1): 30-37.

• 催化剂 • 上一篇    下一篇

ZSM-22催化乙烯叠合制备燃料油的研究

伏朝林,赵杰,赵丽萍,邢恩会,汪燮卿   

  1. 中石化石油化工科学研究院有限公司
  • 收稿日期:2022-06-06 修回日期:2022-07-26 出版日期:2023-01-12 发布日期:2023-01-16
  • 通讯作者: 赵丽萍 E-mail:zhaolp.ripp@sinopec.com
  • 基金资助:
    CO2吸附和直接制备喷气燃料工艺技术探索

STUDY ON THE PERFORMANCE OF ZSM-22 FOR CATALYZING ETHYLENE OLIGOMERIZATION TO LIQUID FUELS

  • Received:2022-06-06 Revised:2022-07-26 Online:2023-01-12 Published:2023-01-16

摘要: 来源于炼油厂的干气、液化气以及生物质或CO2转化制得的低碳烯烃经叠合反应可制备清洁的高品质液体燃料。以乙烯为低碳烯烃代表物,分别考察ZSM-22以及经四乙基氢氧化铵(TEAOH)改性处理的ZSM-22-A催化剂对乙烯叠合制备燃料油的作用并同时对反应条件进行了考察。结果发现,TEAOH改性具有脱硅扩孔、增多酸量的作用,ZSM-22-A表现出了更高的催化活性。该反应合适的温度为280 ℃,压力为5 MPa,质量空速为0.15 ~1.35 h-1(根据油品目标进行选择)。进一步考察了两种催化剂的稳定性,发现ZSM-22在反应280 h后开始出现失活,而ZSM-22-A在反应400 h后仍未失活,具有更高的稳定性,表明利用TEAOH改性ZSM-22对于乙烯叠合制备液体燃料具有良好的应用前景。

关键词: 乙烯, 烯烃叠合, ZSM-22, 改性, 四乙基氢氧化铵, 液体燃料

Abstract: Clean and high-quality liquid fuels could be prepared from low-carbon olefins derived from refinery dry gas, liquefied petroleum gas and biomass or CO2 conversion by the oligomerization reaction. ZSM-22 and ZSM-22-A, modified by tetraethylammonium hydroxide (TEAOH), were used as the catalysts, using ethylene as the representative of low-carbon olefin. Their effects on the synthesis of fuel oil from ethylene and the reaction conditions were investigated, respectively. The results showed that TEAOH modified ZSM-22-A exhibited higher catalytic activity than ZSM-22 due to its desilication, pore enlargement and increase of acid content. The optimum reaction conditions for this reaction were: a reaction temperature of 280 ℃, a reaction pressure of 5 MPa, and a mass space velocity of 0.15 - 1.35 h-1 according to the oil target. It was found that ZSM-22 began to deactivate after 280 h of reaction, but ZSM-22-A did not deactivate after 400 h of reaction, so the ZSM-22-A had higher stability than ZSM-22, which indicated that the modification ZSM-22 with TEAOH had a good application prospect in the synthesis of liquid fuels by ethylene oligomerization.

Key words: ethylene, oligomerization, ZSM-22, modification, tetraethylammonium hydroxide, liquid fuel